CN107641070B - Preparation method of 9, 10-asymmetric disubstituted anthracene derivative - Google Patents
Preparation method of 9, 10-asymmetric disubstituted anthracene derivative Download PDFInfo
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Abstract
The invention discloses a new two-step synthesis method for preparing a 9, 10-asymmetric disubstituted anthracene derivative. Compared with a three-step synthesis method frequently used in literatures, the novel synthesis method has the advantages of short path and low cost, can well control the purity of a final product, and can remarkably improve the purity of the product. The new synthesis method of the invention has high commercial value.
Description
Technical Field
The invention relates to a novel preparation method of a 9, 10-asymmetric disubstituted anthracene derivative, wherein the asymmetric anthracene derivative is widely applied to a blue fluorescence main body and an electron transport material in an OLED (organic light emitting diode) device.
Background
With the continuous advance of OLED technology in two fields of lighting and display, people pay more attention to the research of core materials of OLED technology, an organic electroluminescent device with good efficiency and long service life is generally the result of fully optimized device structure and collocation of high-quality organic materials, the cost of the organic materials also greatly influences the price of an OLED screen body, which is also a key factor influencing the competitiveness of OLED technology, and therefore the high-efficiency, low-cost and high-quality synthesized OLED material has very important significance.
The anthracene derivative has excellent photochemical physical properties, can be widely applied to organic electroluminescent devices, can be used as a fluorescent luminescent material (light-emitting patents CN200480008768, CN201010121028 and CN200510084528) and a main body material (kodak patents US 5935721; US6465115 and WO 2014141725; WO2015033559), and can also be used as an electron transport material (light-emitting patents WO 2014129048; US 2013306955; LG chemical patents WO 2003060956; Wittinger patents CN 200009188449), and greatly improves the performance of corresponding devices, so that the anthracene derivative is a very important OLED material.
The following two methods are mainly used for synthesizing anthracene derivatives: 1. nucleophilic addition of an organic lithium reagent or an organic magnesium reagent and anthraquinone to obtain a diol intermediate, and then reducing the diol intermediate to generate a 9, 10-disubstituted anthracene derivative (Synthesis,45(20), 2913) -2918; 2013; CN 101967079); 2. organic boric acid and 9-bromoanthracene are subjected to Suzuki coupling reaction to obtain 9-substituted anthracene, then 9-substituted-10-bromoanthracene intermediate is generated through bromination, and then the intermediate and another boric acid are subjected to Suzuki coupling reaction to obtain a final product (CN 102936184). The two methods have respective advantages and disadvantages, the method 1 can only be used for synthesizing symmetrical disubstituted anthracene derivatives, and is difficult to realize for asymmetric compounds, the method 2 can be used for preparing various types of disubstituted anthracene derivatives, but three-step synthesis (excluding the step of preparing boric acid) is required, expensive noble metal palladium is required as a catalyst in two steps, the cost is higher, and in addition, for 9-position and 10-position of anthracene, side reaction for removing boric acid or bromine atoms is easy to occur in the coupling reaction due to steric hindrance caused by hydrogen atoms on two sides, so that a plurality of byproducts are generated in the reaction process, the purity of the final product is greatly influenced, the post-treatment cost is improved, and the product with high purity is not easy to obtain.
Anthraquinone process for preparing 9, 10-disubstituted anthracene
Two-step Suzuki coupling method for preparing 9, 10-disubstituted anthracene
In conclusion, the development of a new, simple and efficient method for synthesizing the derivative of the disubstituted anthracene, particularly the asymmetric disubstituted anthracene, has great significance for the development and application fields of OLED materials.
Disclosure of Invention
In order to solve the problems, the invention provides a 9, 10-asymmetric disubstituted anthracene derivative, which comprises anthrone, halogenated aromatic hydrocarbon E, halogenated aromatic hydrocarbon F, a palladium catalyst precursor, an organic phosphine ligand, alkali and a solvent, wherein the synthetic route is as follows:
the 9, 10-asymmetric disubstituted anthracene derivative has the advantages of short synthetic route, easy purification of products, low cost and the like.
The novel synthesis method of the invention comprises the following two steps:
(1) adding raw materials of anthrone, halogenated aromatic hydrocarbon (heteroarene), a catalyst palladium compound, an organic phosphine ligand, alkali and a solvent into a container subjected to drying and nitrogen replacement, wherein the molar ratio of the anthrone to the halogenated aromatic hydrocarbon is 1: 0.95-1: 1.5, and the molar ratio of the anthrone to the catalyst palladium compound and the organic phosphine ligand is as follows: 100:0.1: 0.1-100: 10:10, wherein the using amount of the solvent is 1-100 ml per gram of anthrone; heating the system to 70-150 ℃ under the protection of nitrogen for reaction, after the reaction is carried out for 2-10 hours, monitoring the reaction process to determine that the reaction is finished, cooling to room temperature, adding saturated sodium bicarbonate solution for quenching reaction, carrying out liquid separation, washing and drying on an organic phase, and purifying the product by a column chromatography method to obtain an intermediate 10-substituted-9-anthrone;
(2) adding a solvent subjected to drying treatment and halogenated aromatic hydrocarbon (heteroarene) into a container subjected to drying and nitrogen replacement, wherein the proportion of the solvent to the halogenated aromatic hydrocarbon (heteroarene) is 1-20ml, cooling a reaction system to-50 to-90 ℃ through a low-temperature bath, and then adding an n-butyl lithium solution and the halogenated aromatic hydrocarbon (heteroarene): the molar ratio of n-butyllithium is 1: 0.9-1: 1.2. After the dropwise addition is finished, the dropwise addition temperature is kept for 0.5-2 h, and complete lithiation is guaranteed. And then adding the obtained 10-substituted-9-anthrone at low temperature (-65-90 ℃), wherein the specific ratio of the halogenated aromatic hydrocarbon (heteroarene) to the 10-substituted-9-anthrone is 1: 1-1: 0.7. After the addition, the reaction system is kept at low temperature for reaction for 0.5-1h, then the temperature is raised to room temperature, the reaction is continued for 1-4 h, excessive 6N diluted hydrochloric acid is added for quenching reaction, then the stirring is continued for 1-4 h at the room temperature, liquid separation and extraction are carried out, organic phases are combined, and after washing and drying, the final product 9, 10-unsymmetrical disubstituted anthracene derivative is obtained through column chromatography separation.
In the coupling reaction, the solvent can be selected from various solvents with weak polarity to strong polarity, and alkyl aromatic hydrocarbon solvents with weak polarity such as toluene, xylene, trimethylbenzene and the like; stronger polarity such as ethers including tetrahydrofuran, 1, 4-dioxane, ethylene glycol dimethyl ether, anisole, etc.; strongly polar solvents such as dimethyl sulfoxide, N-dimethylformamide, N-methylpyrrolidone and the like, preferably less polar solvents to avoid side reactions occurring on the O atom, and more preferably solvents such as toluene, xylene and the like.
The anthrone may or may not have a substituent in the coupling reaction, and examples of the substituent include 2-methyl-9-anthrone, 3-methyl-9-anthrone, 2, 6-diphenyl-9-anthrone and the like.
The electrophilic reagent used in the coupling reaction is selected from the group consisting of aromatic (hetero aromatic) chloride, bromide, iodide, trifluoromethanesulfonate, p-toluenesulfonate, methanesulfonate and the like, preferably bromide and iodide.
The palladium catalyst precursor used is selected from palladium chloride, palladium acetate, tetratriphenylphosphine palladium, bis (triphenylphosphine) palladium dichloride, bis (dibenzylideneacetone) palladium, tris (dibenzylideneacetone) dipalladium and the like, preferably bis (dibenzylideneacetone) palladium and tris (dibenzylideneacetone) dipalladium.
The base used in the coupling reaction is selected from various inorganic bases including sodium carbonate, potassium phosphate, potassium fluoride, cesium fluoride, potassium acetate, potassium hydroxide, sodium hydroxide, etc., and organic bases; the organic base includes sodium tert-butoxide, potassium tert-butoxide, lithium bis (trimethylsilyl) amide (LiHMDS) and the like, and sodium tert-butoxide is preferred as the base.
The organophosphorus ligands used in the reaction include various types of alkyl and aryl phosphine derivatives selected from triphenylphosphine, tris (o-methylphenyl) phosphine, tri-tert-butylphosphine, tricyclohexylphosphine, [1,1' -bis (diphenylphosphino) ferrocene, 2-biphenyls or phos-type phosphorus ligands (S-phos, John-phos, X-phos, Dave-phos, DPEphos, Xantphos, etc.), with tri-tert-butylphosphine and tricyclohexylphosphine being preferred.
The molar ratio of the reactants to the palladium procatalyst and the organophosphine ligand may be from 100:0.01:0.01 to 100:10:10, preferably 100:0.1:0.1 to 100:1: 1; wherein the ratio of the palladium to the phosphine ligand is 1: 0.5-1: 4, preferably 1: 1-1: 2.
In the second addition reaction, the solvent used is selected from various solvents which do not react with the organometallic reagent, including hydrocarbons such as petroleum ether, n-hexane, n-pentane, cyclohexane, n-heptane, decahydronaphthalene, etc., aromatic hydrocarbon solvents such as benzene, toluene, xylene, etc., ethers such as diethyl ether, methyl tert-butyl ether, tetrahydrofuran, 1, 4-dioxane, ethylene glycol dimethyl ether, phenyl ether, etc.; toluene, methyl tert-butyl ether and tetrahydrofuran are preferred.
The organometallic reagent is selected from various organometallic reagents which can perform a metal-halogen exchange reaction with the halogenated aromatic hydrocarbon or halogenated heteroarene, including isopropyl magnesium chloride, isopropyl magnesium bromide, tert-butyl magnesium chloride, n-butyl lithium, sec-butyl lithium, tert-butyl lithium and the like; n-butyllithium and tert-butyllithium are preferred.
The novel synthesis method of the invention has the following advantages:
1. the synthesis method can synthesize various asymmetric 9, 10-disubstituted anthracene derivatives, and has wide applicability;
2. the raw materials are simple and easy to obtain, and the anthrone, the halogenated aromatic hydrocarbon or the halogenated heteroarene (aryl or heteroaryl sulfonate and the like) are common and cheap organic raw materials;
3. the reaction steps are short, only two steps of reaction are needed, and compared with a common three-step reaction method (not including the preparation step of corresponding boric acid) for preparing the asymmetric 9, 10-asymmetric disubstituted anthracene derivative, the reaction steps are greatly reduced;
4. only one-step reaction needs a noble metal catalyst, and an organic boric acid raw material is not needed, so that the synthesis cost is obviously reduced;
5. the possible byproducts generated in the reaction process can not be further reacted or have great difference with the structural characteristics of the final product, so that the byproducts can be easily separated and removed from the product, the post-treatment and purification cost can be reduced, and the high-purity final product can be finally obtained. The following shows a series of by-products which may appear during the reaction, and it can be clearly seen that the by-products generated during these intermediate processes have a very large structural difference from the target compound, and thus can be easily removed from the final product, which is also confirmed from the actual experimental process.
By-products which may occur in the synthesis process of the present invention
In conclusion, the synthesis method disclosed by the invention has a good practical effect on preparing the 9, 10-asymmetric disubstituted anthracene derivative with high efficiency and low cost, and has an important significance on improving the application of the derivative in the field of OLEDs.
Detailed Description
The preparation process described in the present invention is described with reference to the following examples. Due to the versatility of the preparation method, the skilled person can easily synthesize various 9, 10-asymmetrically disubstituted anthracene derivatives by known functional group conversion methods based on these preparation methods.
Various chemicals used in the present invention, such as petroleum ether, toluene, tetrahydrofuran, dichloromethane, acetone, sodium tert-butoxide, n-butyllithium, tri-tert-butylphosphine, anthrone, palladium acetate, 2-bromonaphthalene, 1- (4-bromophenyl) naphthalene, 2- (4-bromophenyl) -1-phenyl-1H-benzo [ d ] imidazole, 2-methyl-9-anthrone, 3-methyl-9-anthrone, 2, 6-diphenyl-9-anthrone, tris (dibenzylideneacetone) dipalladium and other basic chemical raw materials, are commercially available in the domestic chemical product market.
Specific examples of the process of the present invention are described below
Synthesis example 1 Synthesis of 9- (1-naphthyl) -10- (2-naphthyl) anthracene (α -ADN)
In a 250ml three-necked flask dried and purged with nitrogen were charged anthrone (19.4g, 0.1mol), 2-bromonaphthalene (24.8g, 0.12 m)mol), sodium tert-butoxide (12.5g, 0.13mol), 150ml of toluene, dissolved with stirring, and Pd (OAc) added2(0.22g, 1mmol) and 10% tri-tert-butylphosphine (4g, 2mmol), heating the reaction system to 100 ℃ under the protection of nitrogen for reaction, after the reaction is finished by monitoring the reaction progress through TLC after 3 hours, cooling to room temperature, adding saturated sodium bicarbonate solution for quenching reaction, extracting the organic phase, separating, washing, combining the organic phase, adding anhydrous sodium sulfate for drying, performing column chromatography by using a petroleum ether/dichloromethane system after the solvent is dried in a spinning mode, and obtaining 27.2 g of 10- (2-naphthyl) -9-anthrone with the yield of 85%.
Adding 1-bromonaphthalene (12.4g, 60mmol) and 150ml of dried THF into a 500ml three-neck flask which is dried and replaced by nitrogen, cooling the reaction system to-78 ℃ by using a dry ice-acetone bath, then adding N-butyllithium solution (45ml, 1.6M hexane solution, 72mmol), after finishing dropping, keeping at-78 ℃ for stirring and reacting for 1h to ensure complete lithiation, then adding 10- (2-naphthyl) -9-anthrone (16g, 50mmol) at-78 ℃, after finishing adding, continuing to react for 0.5h at-78 ℃, then raising to room temperature, continuing to react for 2h, slowly adding excessive 6N dilute hydrochloric acid under cooling of an ice water bath to quench the reaction, then continuing to stir for 2h at room temperature, separating and extracting, combining organic phases, washing, drying, draining the solvent to obtain a white-like solid, and performing toluene recrystallization to obtain a product which is separated by column chromatography, and finally obtaining α -ADN, 19.3 g, 90% yield and purity of more than 99.5%.
1H NMR(500MHz,Chloroform)δ8.01-8.13(m,5H),7.92-7.96(m,2H),7.56-7.78(m,7H),7.43-7.52(m,3H),7.17-7.31(m,5H)。
Elemental analysis data: c, 94.79; h,5.23
Synthesis example 2: synthesis of 9- (4- (1-naphthyl) phenyl) -10- (2-naphthyl) anthracene
In a dry, nitrogen-purged 250ml three-necked flask were charged anthrone (19.4g, 0.1mol), 2-bromonaphthalene (24.8g, 0.12mmol), sodium t-butoxide (12.5g, 0.13mol), 150 molml toluene, dissolved with stirring, then Pd (OAc) is added2(0.22g, 1mmol) and 10% tri-tert-butylphosphine (4g, 2mmol), heating the reaction system to 100 ℃ under the protection of nitrogen for reaction, after the reaction is finished by monitoring the reaction progress through TLC after 3 hours, cooling to room temperature, adding saturated sodium bicarbonate solution for quenching reaction, extracting the organic phase, separating, washing, combining the organic phase, adding anhydrous sodium sulfate for drying, performing column chromatography by using a petroleum ether/dichloromethane system after the solvent is dried in a spinning mode, and obtaining 27.2 g of 10- (2-naphthyl) -9-anthrone with the yield of 85%.
1- (4-bromophenyl) naphthalene (17g, 60mmol) and 150ml of dried THF were charged into a 500ml three-necked flask which had been dried and purged with nitrogen, the reaction system was cooled to-78 ℃ with a dry ice-acetone bath, and then an n-butyllithium solution (45ml, 1.6M hexane solution, 72mmol) was added thereto, and after completion of the dropwise addition, the reaction was stirred at-78 ℃ for 1 hour to ensure completion of lithiation. Then adding 10- (2-naphthyl) -9-anthrone (16g, 50mmol) at-78 ℃, continuing to react for 0.5h at-78 ℃ after the addition is finished, then heating to room temperature, continuing to react for 2h, slowly adding excessive 6N diluted hydrochloric acid under the cooling of ice water bath to quench the reaction, then continuing to stir for 2h at room temperature, separating and extracting, combining organic phases, washing and drying, draining the solvent to obtain a white-like solid, recrystallizing the solvent by toluene to obtain a product, and separating by column chromatography to obtain a final product 23.6g, wherein the yield is 93%, and the purity is more than 99.5%.
1H NMR(500MHz,Chloroform)δ8.24-8.30(m,1H),8.18(d,J＝10Hz,1H),8.08-8.12(m,2H),7.96-8.03(m,5H),7.81-7.84(m,4H),7.62-7.73(m,9H),7.48-7.52(m,2H),7.40-7.44(m,2H).
Elemental analysis data: c, 94.79; h,5.20
Synthetic example 3: synthesis of 2- (4- (10- (2-naphthyl) phenyl) -9-anthryl) -1-phenyl-1H-benzo [ d ] imidazole
In a 250ml three-necked flask dried and purged with nitrogen were charged anthrone (19.4g, 0.1mol), 2-bromonaphthalene (24.8g, 0.12mmol), t-butyl acetateSodium alkoxide (12.5g, 0.13mol), 150ml toluene, dissolved with stirring, then Pd (OAc)2(0.22g, 1mmol) and 10% tri-tert-butylphosphine (4g, 2mmol), heating the reaction system to 100 ℃ under the protection of nitrogen for reaction, after the reaction is finished by monitoring the reaction progress through TLC after 3 hours, cooling to room temperature, adding saturated sodium bicarbonate solution for quenching reaction, extracting the organic phase, separating, washing, combining the organic phase, adding anhydrous sodium sulfate for drying, performing column chromatography by using a petroleum ether/dichloromethane system after the solvent is dried in a spinning mode, and obtaining 27.2 g of 10- (2-naphthyl) -9-anthrone with the yield of 85%.
In a 500ml three-necked flask after drying and nitrogen replacement, 2- (4-bromophenyl) -1-phenyl-1H-benzo [ d ] imidazole (20.9g, 60mmol) and 150ml of dried THF were added, the reaction system was cooled to-78 ℃ with a dry ice-acetone bath, and then n-butyllithium solution (45ml, 1.6M hexane solution, 72mmol) was added, and after completion of the dropwise addition, the reaction was stirred at-78 ℃ for 1 hour to ensure complete lithiation. Then adding 10- (2-naphthyl) -9-anthrone (16g, 50mmol) at-78 ℃, continuing to react for 0.5h at-78 ℃ after the addition is finished, then heating to room temperature, continuing to react for 2h, slowly adding excessive 6N diluted hydrochloric acid under the cooling of ice water bath to quench the reaction, then continuing to stir for 2h at room temperature, separating and extracting, combining organic phases, washing and drying, draining the solvent to obtain a white-like solid, recrystallizing the solvent by toluene to obtain a product, and separating the product by column chromatography to obtain a final product of 25.4 g, wherein the yield is 89%, and the purity is more than 99.5%.
1H NMR(500MHz,Chloroform)δ8.06(d,J＝8Hz,1H),8.0-8.02(m,1H),7.96-7.98(m,2H),7.89-7.91(m,1H),7.82-7.87(m,2H),7.67-7.72(m,4H),7.57-7.62(m,5H),7.52-7.54(m,1H)，7.43-7.51(m,4H),7.37-7.41(m,1H),7.28-7.34(m,6H)。
Elemental analysis data: c, 89.74; h, 4.91; n:4.81
Synthetic example 4: synthesis of 2-methyl-9, 10- (2-naphthyl) anthracene (MADN)
After drying and nitrogen displacementA250 ml three-necked flask was charged with 2-methylanthrone (20.8g, 0.1mol), 2-bromonaphthalene (24.8g, 0.12mmol), sodium tert-butoxide (12.5g, 0.13mol) and 150ml of toluene, stirred to dissolve, and then added with Pd2(dba)3(0.48g, 0.5mmol) and 10% tri-tert-butylphosphine (4g, 2mmol), heating the reaction system to 100 ℃ under the protection of nitrogen for reaction, after the reaction is finished by monitoring the reaction progress through TLC after 3 hours, cooling to room temperature, adding saturated sodium bicarbonate solution for quenching reaction, extracting an organic phase, separating liquid, washing, combining the organic phase, adding anhydrous sodium sulfate for drying, performing column chromatography by using a petroleum ether/dichloromethane system after solvent is dried in a spinning mode, and obtaining 25 g of 2-methyl-10- (2-naphthyl) -9-anthrone with the yield of 80%.
2-bromonaphthalene (12.3g, 60mmol) and 150ml of dried THF are added into a 500ml three-necked flask which is dried and replaced by nitrogen, the reaction system is cooled to-78 ℃ by a dry ice-acetone bath, then n-butyllithium solution (45ml, 1.6M hexane solution, 72mmol) is added, and after the dropwise addition is completed, the reaction is kept at-78 ℃ for stirring reaction for 1h to ensure complete lithiation. Then adding 2-methyl-10- (2-naphthyl) -9-anthrone (16.7g, 50mmol) at-78 ℃, continuing to react for 0.5h at-78 ℃, then heating to room temperature, continuing to react for 2h, slowly adding excessive 6N dilute hydrochloric acid under cooling of ice water bath to quench reaction, then continuing to stir for 2h at room temperature, separating and extracting, combining organic phases, washing and drying, draining the solvent to obtain a white-like solid, recrystallizing the white-like solid by toluene to obtain a final product, namely MADN, 19.8 g, the yield of 89%, and the purity of more than 99.2%.
1H NMR(500MHz,Chloroform)δ8.16-8.23(m,2H),8.02-8.11(m,4H),7.91-8.01(m,3H),7.50-7.66(m,9H),7.35-7.40(m,2H),7.29-7.33(m,1H),2.65(s,3H)。
Elemental analysis data: c, 94.65; h, 5.31.
Synthesis example 5: synthesis of 5- (2-methyl-10- (9-phenanthryl) anthracen-9-yl-2-phenylpyridine
A250 ml three-necked flask dried and purged with nitrogen was charged with 3-methylanthrone (20.8g, 0.1mol), 2-bromonaphthalene (28.1g, 0.12mmol), sodium tert-butoxide (12.5g, 0.13mol), and 150ml of toluene, and stirredDissolving, then adding Pd (dba)2(0.58g, 1mmol) and 10% tri-tert-butylphosphine (4g, 2mmol), heating the reaction system to 100 ℃ under the protection of nitrogen for reaction, after the reaction is finished after 3 hours through TLC monitoring of the reaction process, cooling to room temperature, adding saturated sodium bicarbonate solution for quenching reaction, extracting the organic phase, separating, washing, combining the organic phases, adding anhydrous sodium sulfate for drying, performing column chromatography by using a petroleum ether/dichloromethane system after the solvent is dried in a spinning mode, and obtaining 30.3 g of 3-methyl-10- (6-phenylpyridine-3-yl) -9-anthrone with the yield of 84%.
9-bromophenanthrene (15.4g, 60mmol) and 150ml of dried THF are added into a 500ml three-necked flask which is dried and replaced by nitrogen, the reaction system is cooled to-78 ℃ by a dry ice-acetone bath, then n-butyllithium solution (45ml, 1.6M hexane solution, 72mmol) is added, and after the dropwise addition is completed, the reaction is kept at-78 ℃ for stirring reaction for 1h to ensure complete lithiation. Then adding 3-methyl-10- (6-phenylpyridine-3-yl) -9-anthrone (18.5g, 50mmol) at-78 ℃, continuing to react for 0.5h at-78 ℃, then heating to room temperature, continuing to react for 2h, slowly adding excessive 6N diluted hydrochloric acid under the cooling of ice water bath to quench the reaction, then continuing to stir for 2h at room temperature, separating and extracting, combining organic phases, washing and drying, draining the solvent to obtain a white-like solid, recrystallizing the toluene to obtain a product, and separating the product by column chromatography to obtain a final product, namely 5- (2-methyl-10- (9-phenanthryl) anthracene-9-yl-2-phenylpyridine 23.8 g, which is the white-like solid, with the yield of 82% and the purity of more than 99.4%.
1H NMR(500MHz,Chloroform)δ9.05-9.11(m,1H),8.93-8.98(m,1H),8.80-8.88(m,1H),8.15-8.38(m,6H),7.96-8.04(m,2H),7.85-7.93(m,2H),7.43-7.75(m,10H)，7.32-7.39(m,1H)，2.70(s,3H)。
Elemental analysis data: c, 92.08; h, 5.23; and N, 2.58.
Synthetic example 6: synthesis of 9- (4- (1,1' -biphenyl) -10- (2-naphthyl)) -2, 6-diphenylanthracene
After being driedA250 ml three-necked flask purged with nitrogen was charged with 2, 6-diphenylanthrone (34.6g, 0.1mol), 2-bromonaphthalene (24.8g, 0.12mmol), sodium tert-butoxide (12.5g, 0.13mol), 150ml of toluene, stirred to dissolve, and then Pd (dba) was added2(0.58g, 1mmol) and 10% tri-tert-butylphosphine (4g, 2mmol), heating the reaction system to 100 ℃ under the protection of nitrogen for reaction, after the reaction is finished by monitoring the reaction progress through TLC after 3 hours, cooling to room temperature, adding saturated sodium bicarbonate solution for quenching reaction, extracting the organic phase, separating, washing, combining the organic phase, adding anhydrous sodium sulfate for drying, performing column chromatography by using a petroleum ether/dichloromethane system after the solvent is dried in a spinning mode, and obtaining 38.8 g of 2, 6-diphenyl-10- (2-naphthyl) -9-anthrone with the yield of 82%.
4-bromobiphenyl (14.0g, 60mmol) and 150ml of dried THF were added to a 500ml three-necked flask which had been dried and replaced with nitrogen, the reaction system was cooled to-78 ℃ with a dry ice-acetone bath, and then n-butyllithium solution (45ml, 1.6M hexane solution, 72mmol) was added, and after completion of the dropwise addition, the reaction was stirred at-78 ℃ for 1 hour to ensure complete lithiation. Then adding 2, 6-diphenyl-10- (2-naphthyl) -9-anthrone (23.6g, 50mmol) at-78 ℃, continuing to react for 0.5h at-78 ℃, then heating to room temperature, continuing to react for 2h, slowly adding excessive 6N dilute hydrochloric acid under the cooling of ice water bath to quench the reaction, then continuing to stir for 2h at room temperature, separating and extracting, combining organic phases, washing and drying, draining the solvent to obtain a white solid, recrystallizing the white solid by toluene to obtain a product, and separating the product by column chromatography to obtain the final product 9- ([4- (1,1' -biphenyl) -10- (2-naphthyl) -2, 6-diphenylanthracene, 26.5 g, the yield is 87%, and the purity is more than 99.3%.
1H NMR(500MHz,Chloroform)δ8.95-9.01(m,2H),8.31-8.39(m,2H),8.03-8.12(m,2H),7.97-8.02(m,1H),7.71-7.80(m,6H),7.34-7.68(m,15H),7.22-7.29(s,4H)。
Elemental analysis data: c, 94.76; h, 5.23.
The above are only some embodiments of the present invention, and it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the inventive concept of the present invention, and these changes and modifications are within the scope of the present invention.
Claims (8)
1. A preparation method for synthesizing 9, 10-asymmetric disubstituted anthracene derivatives is characterized by comprising the following steps: the method comprises the following steps:
(1) adding raw materials of anthrone, halogenated aromatic hydrocarbon, a catalyst palladium compound, an organic phosphine ligand, alkali and a solvent into a container subjected to drying and nitrogen replacement, wherein the ratio of the anthrone to the halogenated aromatic hydrocarbon is 1: 0.95-1: 1.5, and the ratio of the anthrone to the catalyst palladium compound and the organic phosphine ligand is as follows: 100:0.1: 0.1-100: 10:10, wherein the using amount of the solvent is 1-100 ml per gram of anthrone;
heating the system to 70-150 ℃ under the protection of nitrogen for reaction, after the reaction is carried out for 2-10 hours, monitoring the reaction process to determine that the reaction is finished, cooling to room temperature, adding saturated sodium bicarbonate solution for quenching reaction, carrying out liquid separation, washing and drying on an organic phase, and purifying the product by a column chromatography method to obtain an intermediate 10-substituted-9-anthrone;
(2) adding a solvent subjected to drying treatment and halogenated aromatic hydrocarbon into a container subjected to drying and nitrogen replacement, wherein the proportion of the solvent subjected to drying treatment to the halogenated aromatic hydrocarbon is 1-20ml, cooling a reaction system to-50 to-90 ℃ through a low-temperature bath, and then adding n-butyl lithium solution and halogenated aromatic hydrocarbon: the molar ratio of n-butyl lithium is 1: 0.9-1: 1.2; after the dropwise addition is finished, keeping the dropwise addition temperature for 0.5-2 h to ensure complete lithiation;
then adding the obtained 10-substituted-9-anthrone at the low temperature of-65 ℃ to-90 ℃, wherein the ratio of the halogenated aromatic hydrocarbon to the 10-substituted-9-anthrone is 1:1 to 1: 0.7;
after the addition, the reaction system is kept at low temperature for reaction for 0.5-1h, then the temperature is raised to room temperature, the reaction is continued for 1-4 h, excessive 6N diluted hydrochloric acid is added for quenching reaction, then the stirring is continued for 1-4 h at the room temperature, liquid separation and extraction are carried out, organic phases are combined, and after washing and drying, the final product 9, 10-unsymmetrical disubstituted anthracene derivative is obtained through column chromatography separation.
2. The process according to claim 1, wherein the synthesis of the 9, 10-unsymmetrically disubstituted anthracene derivative is carried out by: in the coupling reaction, the solvent may be selected from a weakly polar to a strongly polar solvent.
3. The process according to claim 1, wherein the synthesis of the 9, 10-unsymmetrically disubstituted anthracene derivative is carried out by: the anthrone may or may not have substituents in the coupling reaction.
4. The process according to claim 1, wherein the synthesis of the 9, 10-unsymmetrically disubstituted anthracene derivative is carried out by: the palladium catalyst precursor used is selected from palladium chloride, palladium acetate, tetratriphenylphosphine palladium, bis (triphenylphosphine) palladium dichloride, bis (dibenzylideneacetone) palladium, tris (dibenzylideneacetone) dipalladium.
5. The process according to claim 1, wherein the synthesis of the 9, 10-unsymmetrically disubstituted anthracene derivative is carried out by: the base used in the coupling reaction is selected from inorganic bases and organic bases.
6. The process according to claim 1, wherein the synthesis of the 9, 10-unsymmetrically disubstituted anthracene derivative is carried out by: organophosphorus ligands useful in the reaction include alkyl and aryl phosphine derivatives.
7. The process according to claim 1, wherein the synthesis of the 9, 10-unsymmetrically disubstituted anthracene derivative is carried out by: the molar ratio of reactants to palladium catalyst precursor and organophosphine ligand is from 100:0.01:0.01 to 100:10: 10.
8. The process according to claim 1, wherein the synthesis of the 9, 10-unsymmetrically disubstituted anthracene derivative is carried out by: in the second addition reaction, the solvent used is selected from solvents which do not react with the organometallic reagent; the organometallic reagent is selected from organometallic reagents that undergo a metal-halogen exchange reaction with a haloarene or haloheteroarene.
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| CN101374789A (en) * | 2006-01-27 | 2009-02-25 | Lg化学株式会社 | New anthracene derivatives, preparation method thereof and organic light emitting diode using the same |
| CN101701152A (en) * | 2008-11-24 | 2010-05-05 | 上海拓引数码技术有限公司 | 9,10-substituted-2,6-di-tert-butyl anthracene blue-ray organic electroluminescent material and preparation method thereof |
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| CN101374789A (en) * | 2006-01-27 | 2009-02-25 | Lg化学株式会社 | New anthracene derivatives, preparation method thereof and organic light emitting diode using the same |
| CN101701152A (en) * | 2008-11-24 | 2010-05-05 | 上海拓引数码技术有限公司 | 9,10-substituted-2,6-di-tert-butyl anthracene blue-ray organic electroluminescent material and preparation method thereof |
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